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To cite this document: Van Baelen, Guy and Vreysen, Steven and Gerbaud,
Vincent and Rodriguez-Donis, Ivonne and Geens, Jeroen and Janssens, Bart
(2010) Isopropyl alcohol recovery by heteroazeotropic batch distillation. In:
European Meeting on Chemical Industry and Environment EMChiE, 17-19 May
2010, Mechelen, Belgium.
Guy Van Baelena, Steven Vreysena*, Vincent Gerbaud b, Ivonne Rodriguez Donisc, Jeroen
Geensd, Bart Janssensa
a
K.H.Kempen University College, Kleinhoefstraat 4, B-2440 Geel
b
CNRS Laboratoire de Génie Chimique, 5 rue Paulin Talabot, F-31078 Toulouse
c
Instituto Superior de Tecnologías y Ciencias Aplicadas (INSTEC), Cuba
d
Janssen Pharmaceutica, Turnhoutseweg 30, B-2340 Beerse
Abstract
Solvent recovery is becoming a major issue in the pharmaceutical and specialty chemical
industries. Solvent recovery by conventional batch distillation is limited by the frequent
presence of azeotropes in the used solvent mixtures. Most distillation processes for the
separation of azeotropic or difficult zeotropic mixtures involve the addition of an entrainer
(homogeneous and heterogeneous azeotropic distillation or extractive distillation).
In this study the recovery of IPA (isopropyl alcohol) from an industrial waste stream
(IPA/water mixture) was studied by conventional batch distillation and heteroazeotropic batch
distillation, using cyclohexane as entrainer. First the ternary IPA/water/cyclohexane azeotrope
(boiling temperature of 64.1 °C), then the binary IPA/cyclohexane azeotrope (boiling
temperature of 69.3°C) and finally pure IPA was distilled.
Keywords:
Solvent recovery, batch distillation, heteroazeotropic distillation, isopropyl alcohol,
dewatering, residue curve map
Solvent recovery is becoming a major issue in the pharmaceutical and specialty chemical
industries. The strongest commercial argument for recovering solvents is the direct cost
savings. In some processes with intensive solvent use, the cost of the solvent can be a
significant proportion of the overall product cost. Another compelling reason for recovering
solvents is the increasing environmental legislation against emissions, some of them being the
result of used solvent incineration.
The active pharmaceutical ingredients business is facing all the time 'small volumes' and
'large and continuously changing product portfolio'. These elements make the use of
'optimized continuous distillation' economically unviable. Either this industry considers
batch-configurations, either they are forced to waste incineration/discharge.
In waste streams, the frequent presence of azeotropes and zeotropic mixtures with a pinch in
the vapor-liquid equilibrium in these streams limit the use of conventional distillation. Most
distillation processes for the separation of azeotropic or difficult zeotropic mixtures involve
the addition of an entrainer. In azeotropic distillation, the entrainer is added to the charge,
whereas it is fed continuously in extractive distillation.
Despite its anteriority to continuous distillation and its interest in high value added industries,
batch distillation processes where not devoted as much attention as they should and for long,
only homogeneous batch distillation was considered. Homogeneous batch extractive
distillation was studied in 1988 by Lelkes et al. [1]; the feasibility of heterogeneous batch
distillation processes was described by Rodriguez Donis et al. in 1992 [2]; pressure swing
batch distillation was investigated in 2008 in by Lang and Modla [3] and a general criterion
for extractive batch distillation was published in 2009 by Rodriguez-Donis et al. [4] and
applied to entrainers that form new azeotrope [5]. In these papers, a major advantage of batch
distillation over continuous distillation is the ability to drive the composition changes in the
column during time thanks to the operating parameters, among which the reflux policy.
In this study the recovery of IPA (isopropyl alcohol) from an industrial waste stream
(IPA/water mixture) is studied by conventional batch distillation and heterogeneous batch
distillation.
Many distillation processes have been proposed to separate a pure substance from a mixture.
There are two kinds of approaches to obtain a nearly pure IPA using advanced continuous
distillation processes. One is to utilize an azeotropic distillation process using benzene or
cyclohexane as an entrainer and the other is an extractive distillation process using ethylene
glycol as a solvent. In azeotropic distillation, by forming a ternary heterogeneous azeotrope
lower than any other binary azeotropic temperatures, a nearly pure IPA can be obtained as a
In this study the recovery of IPA from an industrial waste stream (IPA/water mixture) was
studied by heterogeneous azeotropic batch distillation with cyclohexane. This technique is
compared with conventional distillation and salting out methods.
According to experimental data [10], IPA forms a homogeneous minimum boiling azeotrope
with cyclohexane at 67.0 mass% (37.8 mole%) and 68.6°C, and a ternary heteroazeotrope at
18.5 mass% (19.1 mole%) and 64.3°C. Finally, cyclohexane forms a heteroazeotrope with
water at 8.5 mass% (31.3 mole%) and 69.8°C. The ternary mixture belongs to the 3.1-2
Serafimov’s class, the most frequent, accounting for 26% of ternary mixtures [11]. The three
pure components, the three binary azeotropes and the ternary azeotrope are stable nodes,
saddle and unstable node respectively. Therefore, azeotropic distillation of any ternary
mixture water – IPA - cyclohexane will lead to the ternary heteroazeotrope as distillate, which
can be further decanted in a cyclohexane-rich phase and in a water-rich phase.
Residue curve
0.9
calculated
LLE conodale
0.7 Experimental
Tmin AzeoWater-IPA LLE conodale
(80.3°C) [s]
calculated VLLE
enveloppe
0.5
Tmin AzeoC6H12-IPA Experimental &
(69.4°C) [s] calculated LLE
enveloppe
0.3
Tmin Azeo
(63.7°C) [UN] 0.1
Figure 1 displays VLLE calculations using the NRTL model and VLE binary parameters from
Dechema [12] and LLE calculations using UNIQUAC with LLE parameters published in the
Dechema [13]. The LLE conodale slopes at 25°C are reasonably predicted but do not capture
the solutrope LLE behavior of the mixture. The VLE calculations agree fairly well, although
they slightly overestimate the IPA fraction in the ternary azeotrope.
EXPERIMENTAL METHOD
An industrial IPA/Water mixture with an IPA content > 97 mass% was used. The IPA was
previously dewatered by sodium hydroxide. The goal is to purify it with less than 0.1% water.
Cyclohexane with a purity ≥ 99% was used.
The water content of the samples was measured with an automatic Karl Fisher titration. The
cyclohexane and IPA content were measured by gas chromatography using pentane as an
internal standard.
CONVENTIONAL DISTILLATION
All conventional distillation tests were executed with a fractioned distillation column with 28
theoretical plates. The adiabatic column with a length of 105 cm and a diameter of 3 cm is
filled with metal rashig rings.
780 g of an IPA/water mixture, which contained 2.00 mass% water was distilled with the
conventional distillation column. The reflux ratio was ∞ until steady state conditions were
reached at the top of the column (boiling temperature of binary IPA/water azeotrope). The
IPA/water azeotrope was distilled with a reflux ratio of 30:2.
SALTED-OUT DISTILLATION
In a second experiment MgSO4 was added as a drying agent to a known amount of IPA/Water
mixture (2.47 mass% water). This mixture was mixed during 0.5h. A small amount of the salt
dissolved in the mixture. The mixture was distilled with the conventional distillation method,
with a reflux ration of 20:2, when equilibrium conditions were reached.
In a third experiment the added MgSO4 was filtered off prior to distillation. The water content
of the initial IPA/water mixture was 1.75 mass%.
HETEROAZEOTROPIC DISTILLATION
The heteroazeotropic distillation is performed on a Heckman column with 30 real plates. 50L
of an IPA/water mixture, which contained 0.83 mass% water and 2.5L of cyclohexane were
added to the reboiler. This cyclohexane amount is slightly larger than the total holdup of the
column (2250 mL). Preliminary test showed that this was the optimal entrainer volume. The
vapor flow rate was set at 0.23 kmol/h.
The reflux ratio was ∞ until steady state conditions were reached at the top of the column
where the recorded temperature was that of the boiling ternary IPA/water/cyclohexane
azeotrope. Then the reflux ratio of the column was set at 30:1. In a second step, the ternary
IPA/water/cyclohexane heteroazeotrope was collected, cooled with ice and transferred to a
seperatory funnel. The water phase was collected and the organic phase was completely
refluxed at the top of the column. This was continued until separation of the two phase
became difficult because of the water removal. Then homogeneous distillation proceeded.
CONVENTIONAL DISTILLATION
Figure 2 shows the temperature of the top vapor and the water content (mass %) of the residue
as a function of the volume distillate. After 27% of the initial volume was distilled with a
conventional distillation, the temperature of the top vapor was 81.9 °C, which corresponds to
pure IPA. The water content of the residue reached the specification of 0.1 mass%.
83 2,5
81
1
80,5
80
0,5
79,5
79 0
0 5 10 15 20 25 30 35
Figure 2 also shows that the distillation curve of the IPA/Water mixture with the addition of
MgSO4 as a drying agent is similar to the distillation curve of the conventional distillation.
The water content of the residue was 0.14 mass%. When the MgSO4 salt was filtered prior to
the distillation, the curve in the distillation line is more pronounced. The water content of the
residue in this case is 0.02 mass%. However, the volume of distillate before the temperature
of the top vapor equals the boiling temperature of IPA is again 25 – 30 %. The IPA recovery
is thus 75 – 70 %.
Figure 3 shows the temperature at the top of the column as a function of time. Because of the
applied reflux policy (total reflux of organic rich phase), it is impossible to plot the top
temperature as a function of volume distillate.
85
IPA
80
75
IPA-
Temperature (°C)
70 Cyclohexane
IPA-Water-
65
Cyclohexane
60
55
50
00:00:00 02:24:00 04:48:00 07:12:00 09:36:00 12:00:00 14:24:00
Time (h)
As predicted from the residue curve map analysis, figure 3 shows that first a distillate with
boiling temperature of 64.1 °C, close to the ternary azeotrope composition is distilled. After
collection 1.69L water phase (at a temperature of 65.2 °C), the separation of the two layers
became difficult. At this point, the decanter is useless and conventional distillation proceeds.
The boiling temperature of 69.3°C indicates that the binary IPA/cyclohexane azeotrope is
distilled until the top temperature was 82.1°C. The total amount of binary azeotrope recovered
was 4L. Finally 500 mL pure IPA is further distilled.
During the transitions between the ternary azeotrope and the binary IPA/cyclohexane
azeotrope, the composition likely moves along the distillation boundary displayed in figure 1.
Table 1 shows the molar fraction and mass percentage of each component in the different
collected samples. The water content in IPA decreases from 0.63 mass% to 0.04 mass%. IPA
with a purity of 99.96 mass% can be obtained. The IPA recovery is 97.6%.
The binary CyH/IPA azeotrope can be reused in a subsequent batch distillation. The CyH in
the water phase cannot be recovered. The total CyH recovery is 90.0%.
Table 2 shows the component molar mass balance of the main streams. The deviation of
molar amount of IPA and water (1.98% and 2.75% relative to the initial composition) is
within the experimental error. The deviation of the molar amount of CyH is larger (-14.97%
relatively to the initial composition). This can be explained by the CyH loss by evaporation,
since the organic and aqueous phase were decanted manually.
Table 2: Component molar mass balance of the main streams of the process
CONCLUSIONS
The IPA recovery could be improved by selecting an entrainer, which does form a minimum
boiling heteroazeotrope with water, but not a ternary azeotrope. Alternatively, according to
literature, recovery could be also improved by refluxing part of the water-rich phase in order
to keep the phase separation longer.
REFERENCES:
[1] Lelkes Z., Lang P., Benadda B. and Moszkowicz P. 1998. Feasibility of Extractive Distillation in a Batch
Rectifier. AIChE Journal, 44 , 810-822.
[2] Rodriguez Donis, I., Gerbaud, V. 2002. Feasibility of Heterogeneous Batch Distillation Processes. AIChE
Journal 48(6), 1168-1178.
[3] Modla G. and Lang P., 2008. Feasibility of new pressure swing batch distillation methods, Chem. Eng. Sci.,
63(11), 2856-2874.
[4] Rodriguez-Donis I., Gerbaud V. and Joulia X., 2009, Thermodynamic Insights on the Feasibility of
Homogeneous Batch Extractive Distillation. 1. Azeotropic Mixtures with Heavy Entrainer. Ind. Eng. Chem.
Res., 48(7), 3544–3559.
[5] Rodriguez-Donis I., Gerbaud V. and Joulia X., 2010, Thermodynamic insight on extractive distillation with
entrainer forming new azeotropes. Proceedings of “Distillation & absorption 2010” (Eindhoven, Pays Bas, 12-
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[10] Lange’s Handbook of Chemistry, 10th edition.
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